共查询到17条相似文献,搜索用时 453 毫秒
1.
对甲基苯胺经甲基化、甲酰化得到5,N,N-三甲基-2-氨基苯甲醛;对L-亮氨酸经酯化、格氏反应得到二齿手性氨基醇.二齿手性氨基醇与上述醛经缩合、还原反应,得到三齿手性氨基醇.产物结构经IR,MS和1H NMR等进行了表征;通过改变主客体的浓度及手性羧酸的纯度,运用1H NMR分别考察了主体二齿手性氨基醇、三齿手性氨基醇对客体布洛芬和扁桃酸对映异构体的手性识别能力.结果表明:当主客体物质的量之比为1:1时,三齿手性氨基醇对布洛芬消旋体的a位甲基质子及扁桃酸消旋体的a位质子分别产生11.2和9.2 Hz的化学位移差值. 相似文献
2.
3.
以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。 相似文献
4.
5.
6-氨基胡椒醛与4',4"(5")-二乙酰基二苯并-18-冠-6进行Friedlander缩合得到新的冠醚衍生物——4',4"(5")-{二-[1,3]二氧[4,5-g]喹啉}-二苯并-18-冠-6(3),产率62%。3的结构经UV,^1H NMR,^13C NMR,IR和MS表征。 相似文献
6.
7.
8.
9.
10.
11.
Atropisomeric (R,R)-2,2'-bi([2]paracyclo[2](5,8)quinolinophane) [(R,R)-1] and (R,R)-1,1'-bi([2]paracyclo[2](5,8)isoquinolinophane) [(R,R)-2] have been prepared in moderate overall yield (17 and 9%, respectively) by a four-step sequence starting from (R)-(-)-4-amino[2.2]paracyclophane and (R)-(-)-4-carboxy[2.2]paracyclophane, respectively. The structures have been determined on the basis of NOE (1)H NMR analysis and molecular mechanics (MM) calculations performed with a Spartan02 program, using the MMF94s force field. A preliminary, qualitative analysis of the chiroptical properties of these two compounds has also been attempted. The main spectral data can be interpreted in terms of an almost planar 2,2'-bisquinoline chromophore inserted in a paracyclophane structure in the case of (R,R)-1, while in the case of (R,R)-2, the main role is played by a distorted 1,1'-bisisoquinoline chromophore. On the basis of the above structural results, a hypothesis about the enantioselection capability of these two molecules has also been formulated. 相似文献
12.
Will R. Henderson Danielle E. Fagnani Jonathan Grolms Khalil A. Abboud Ronald K. Castellano 《Helvetica chimica acta》2019,102(4)
A series of [2.2]paracyclophane‐bisamide regioisomers and alkylated comparators were designed, synthesized, and characterized in order to better understand the transannular hydrogen bonding of [2.2]paracyclophane‐based molecular recognition units. X‐Ray crystallography shows that transannular hydrogen bonding is maintained in the solid‐state, but no stereospecific self‐recognition is observed. The assignment of both transannularly and intermolecularly hydrogen bonded N?H stretches could be made by infrared spectroscopy, and the effect of transannular hydrogen bonding on amide bond rotation dynamics is observed by 1H‐NMR in nonpolar solvents. The consequences of transannular hydrogen bonding on the optical properties of [2.2]paracyclophane is observed by comparing alkylated and non‐alkylated pseudo‐ortho 4,12‐[2.2]paracyclophane‐bisamides. Finally, optical resolution of 4‐mono‐[2.2]paracyclophane and pseudo‐ortho 4,12‐[2.2]paracyclophane‐bisamides was achieved through the corresponding sulfinyl diastereoisomers for circular dichroism studies. Transannular hydrogen bonding in [2.2]paracyclophane‐amides allows preorganization for self‐complementary intermolecular assembly, but is weak enough to allow rapid rotation of the amides even in nonpolar solvents. 相似文献
13.
《Tetrahedron: Asymmetry》2001,12(4):529-532
A series of novel planar chiral N,O-[2,2]paracyclophane ligands were synthesised and applied as catalysts in the enantioselective addition of diethylzinc to aldehydes. The results indicate that the planar chirality of [2,2]paracyclophane, not the central chirality of the oxazoline, is the dominant stereocontrolling element. 相似文献
14.
设计合成了3种源于脯氨酸的手性乙炔基单体——(S)-2-乙炔基-N-芳香胺基甲酰基吡咯烷. 在氯化降冰片二烯铑二聚体{[Rh(nbd)Cl]2}-三乙胺催化下, 3种单体被转化为相应的光学活性螺旋聚合物. 用高效液相色谱评估了3种聚合物作为手性固定相(CSPs)对9种底物的手性识别性能. 以正己烷/异丙醇(体积比9∶1)为流动相时, 3种聚合物对3对种氢键给体分子苯偶姻(α=1.35~1.44)、 三氟-1-(9-蒽基)乙醇(α=1.11~1.53)、 2,2′-二羟基-1,1′-联萘(α=1.09~1.11)及乙酰丙酮钴(α=1.84~2.38)表现出很好的手性识别能力; 当以正己烷为流动相时, 3种聚合物都能立体选择性地识别氢键给体分子2,2-二甲基-1-苯基-1-丙醇(α=1.12~1.22), 聚[(S)-2-乙炔基-N-(2′-萘基胺基甲酰基)吡咯烷]能识别氢键受体分子2-苯基环己酮(α=1.11). 结合核磁共振波谱、 拉曼光谱、 旋光测试、 紫外吸收光谱和圆二色光谱及液相色谱等方法, 系统研究了芳香侧基结构与连接位置对聚合物螺旋构象和对映体选择性拆分能力的影响. 分子对接模拟结果表明, 1-萘基的空间位阻大于2-萘基且可促进形成更强的分子内氢键, 不利于大尺寸底物(如联萘酚)的手性拆分. 与苯基相比, 引入萘基有利于增强聚合物与底物间的π-π相互作用, 提高聚合物的立体选择性和手性识别能力. 相似文献
15.
1H-1H scalar coupling across two stacked (parallel and eclipsed) aromatic rings has been revealed through the 1D and 2D 1H NMR analysis of a [2,2]paracyclophane and rationalized by means of density functional theory (DFT) calculation of the J values. 相似文献
16.
Gruselle M Thouvenot R Malézieux B Train C Gredin P Demeschik TV Troitskaya LL Sokolov VI 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4763-4769
The ferrocenic ammonium (Rp)- and (Sp)-[1-CH2NR(3-)-2-CH3-C5H3Fe-C5H5] iodide salts with R=CH3, C2H5, n-C3H7, n-C4H9, were synthesized starting from the (Rp)- and (Sp)-[1-CH2N(CH3)2-2-CH3-C5H3Fe-C5H5] amines obtained in their optically active forms through asymmetric cyclopalladation of [C5H5Fe-C5H4CH2N(CH3)2]. 1H NMR studies of these planar chiral 1,2-disubstituted ferrocenic ammonium iodide salts in the presence of the (Delta)-(tris(tetrachlorobenzenediolato)phosphate(V) anion), [(Delta)-Trisphat] support the formation of specific diastereomeric ion pairs. Such intermolecular interactions can be related to the self-assembly of the two-dimensional optically active compounds [[(Sp)-1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5][Mn (Delta)-Cr(C2O4)3]] and [[(Rp)-1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5][Mn (Lambda)-Cr(C2O4)3]] starting from the resolved (Rp)- and (Sp)-[1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5]+ ion associated to the racemic anionic building block rac-[Cr(C2O4)3]3- and Mn2+. Both enantiomeric forms of the networks behave as ferromagnets with a Curie temperature of 5.7 K. 相似文献